W. Krämer, E. Geyer and D. Schollmeyer

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ζ . Kristallogr. N C S 2 1 3 ( 1 9 9 8 ) 7 8 7 - 7 8 8 7 8 7

Crystal structure of l,7-dihydroxytricyclo[5.3.1.1^'^]dodeca-4,9-dien- 3,8,ll,12-tetraone, C20H24O6

W. Krämer, E. Geyer and D. Schollmeyer

Universität Mainz. Institut für Organische Chemie, Saarstraße 21. D-55099 Mainz, Germany

Received June 2, 1998, CSD-No. 409315

Fig. 1. One of the three independent molecules.

Fig. 2. Projection of the unit cell, view along [100].

S o u r c e of m a t e r i a l : T h e o x i d a t i o n o f 4 , 6 - d i e t h y l p y r o g a l i o l l e a d s - in d e p e n d e n c e o n t h e c o n d i t i o n of t h e r e a c t i o n - t o d i f f e r e n t d i m e r 3 - h y d r o x y - o - q u i n o n e s . In all it e x i s t s 4 d i f f e r e n t s t r u c t u r e s ( s e e r e f . 1 ). B y u s i n g p o t a s s i u m n i t r o s o d i s u l f o n a t e in a q u e o u s m e d i a a t p H = 8 l , 7 - d i h y d r o x y t r i c y c l o [ 5 . 3 . 1 . 1 ^ ' ^ d o d e c a - 4 , 9 4 l i e n - 3 , 8 , 1 1 , 1 2 - t e t r a o n e will b e o b t a i n e d . C r y s t a l s w e r e o b t a i n e d t h r o u g h s l o w c r y s t a l l i z a t i o n f r o m e t h e r . T h e p o s i t i o n of t h e c a r b o n y l b r i d g e s h a v e b e e n c l a r i f i e d b y X - r a y d i f f r a c t i o n .

С2(Л240б, triclinic, PI ( N o . 2), α =9.1321(1) Â, ¿? =12.4632(2) Λ , с = 1 3 . 9 1 3 4 ( 3 ) Â , α =109.363(2)°, β =1(Ϊ7.123(2)°, γ= 9 4 . 7 4 2 ( 2 ) ° , ν = 1 3 9 9 . 0 Â ^ Ζ = 3 , R(F} =0.(Μ5, Ry^F^) = 0 . 1 3 2 .

Table 1. Parameters used for the X-ray data collection

Ciystal: colorless block, size 0.26 χ 0.26 χ 0.42 mm Wavelength: Cu «Γα radiation (1.54180 Â)

μ: 7.80 cm"'

Diffiractometer: Enraf-Nonius CAD4 Scan mode: οι/2β Tmeasurrnuiu'· 298 К

2θ™,χ: 140.04°

5286

Criterion for/о: / ο > 2 σ ( / ο ) Ν(ραΓαηι)Γφκά: 379

Programs: SIR92, SHELXL-97, CELSIUS, Corine

Table 2. Final atomic coordinates and displacement parameters (in A^)

Atom Site X У ζ í/iso

H(2A) 2/ 0.5206 0.0939 -0.1765 0.067(7) H(5A) 2i 0.7211 0.0736 0.2343 0.042(5) H(7A) 2i 0.7729 -0.1253 0.1315 0.050(4) H(7B) 2i 0.7679 -0.1482 0.0127 0.050(4) H(8A) 2i 1.0209 -0.0604 0.1331 0.076(4) H(8B) 2i 0.9596 0.0459 0.1948 0.076(4) H(8C) 2i 0.9544 0.0232 0.0760 0.076(4) H(9A) 2i 0.6982 0.3549 0.2701 0.097(7) H(9B) 2i 0.5590 0.2925 0.2884 0.097(7) H(IOA) 2i 0.7784 0.3484 0.4395 0.18(1) H(IOB) 2i 0.8697 0.2744 0.3712 0.18(1) H(IOC) 2i 0.7299 0.2126 0.3900 0.18(1) H(2B) 2i 0.3257 0.0220 0.2572 0.093(9) H(5B) 2i 0.6925 0.2317 0.6681 0.050(5) H(7C) 2i 0.8716 0.0844 0.6863 0.072(5) H(7D) 2i 0.8581 -0.0172 0.5795 0.072(5) H(8D) 2i 1.0529 0.1359 0.6153 0.099(6) H(8E) 2i 0.9326 0.2186 0.6137 0.099(6) H(8F) 2i 0.9192 0.1168 0.5066 0.099(6)

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788

C20H24O6

Table 2. (Continued) Table 2. (Continued)

Atom Site X У ζ t/iso Atom Site X у ζ i/iso

H(91A) 2i 0.5533 0.3783 0.6604 0.102(9) Н(5С) 2/ 0.3111 0.4363 0.0910 0.040(5)

H(91B) 2i 0,4971 0.3799 0.5433 0.102(9) Н(7Е) li 0.2123 0.5162 -0.1409 0.048(4)

H(92A) 2i 0.3689 0.3275 0.5773 0.102(9) H(7F) 2i 0.3533 0.5435 -0.0340 0.048(4)

H(92B) 2i 0.5351 0.3688 0.6651 0.102(9) H(8G) li 0.3761 0.3853 -0.1720 0.073(4)

H(IOD) 2i 0.3105 0.4180 0.6190 0.171 Н(8Н) li 0.2130 0.3175 -0.1876 0.073(4)

H(IOE) 2i 0.3049 0.2997 0.6360 0.171 Н(81) li 0.3546 0.3451 -0.0806 0.073(4)

H(IOF) 2i 0.2484 0.3006 0.5185 0.Ι7Ι Н(9Е) li 0.2912 0.3330 0.2009 0.064(5)

H(llD) 2i 0.4810 0.4868 0.5891 0.160 H(9F) li 0.1413 0.2346 0.1509 0.064(5)

H(llE) 2i 0.4533 0.3909 0.4753 0.160 H(IOG) li 0.1741 0.3434 0.3308 0.125(7)

H(llF) 2i 0.6207 0.4325 0.5637 0.160 H(IOH) li 0.0183 0.3580 0.2550 0.125(7)

H(2C) 2i -0.3212 0.2791 -0.0968 0.084(8) H(IOI) li 0.1680 0.4565 0.3050 0.125(7)

Table 3. Final atomic coordinates and displacement parameters (in Â^)

Atom Site X У ζ Un f/22 Í/33 Ul2 U,3 U23

2У 2i 2i li 2i 2i 2i 2i CKIA) 0(2A) 0(3A) C(1A) C(2A) C(3A) C(4A) C(5A)

C(6A) 2i

C(7A) 2i C(8A) C(9A) C(IOA) 2/

0(1B) 2i

0(2B) 0(3B) C(1B) C(2B) C(3B) C(4B) C(5B) C(6B) C(7B) C(8B) C(9B) C(IOB) 2i C(llB) 2i 0(1C) 2Í 0(2C) 0(3C) C(1C) C(2C) C(3C) C(4C) C(5C) C(6C) C(7C) C(8C) C(9C)

2/

2i

C(IOC) 2i

0.5133(1) 0.5123(1) 0.7045(1) 0.5519(2) 0.5171(2) 0.6361(2) 0.6492(2) 0.6731(2) 0.6312(2) 0.7813(2) 0.9441(2) 0.6590(3) 0.7690(4) 0.3363(2) 0.3769(2) 0.6772(2) 0.4181(2) 0.4307(2) 0.6015(2) 0.6652(2) 0.6290(2) 0.5137(2) 0.8409(2) 0.9459(3) 0.4796(4) 0.3226(6) 0.511(2) -0.1425(1) -0.2745(1) -0.0534(1) -0.0574(2) -0.1293(2) -0.0166(2) 0.1447(2) 0.2034(2) 0.1134(2) 0.2592(2) 0.3049(2) 0.1780(2) 0.1302(4)

0.2939(1) 0.14945(9) -0.0056(1)

0.2028(1) 0.1020(1) 0.0243(1) -0.0199(1) 0.0821(1) 0.1837(1) -0.0878(2) -0.0129(2) 0.2850(2) 0.2796(3) 0.1757(2) -0.0351(1) -0.0298(1) 0.1421(2) 0.0138(2) 0.0084(2) 0.0592(2) 0.1796(2) 0.2174(2) 0.0611(2) 0.1403(3) 0.3375(2) 0.3391(4) 0.417(1) 0.2587(1) 0.3301(1) 0.3719(1) 0.3315(1) 0.3927(1) 0.4092(1) 0.4795(1) 0.4251(1) 0.3621(1) 0.4874(2) 0.3733(2) 0.3180(2) 0.3741(3)

0.0760(1) -0.11383(8) -0.08837(9) 0.0741(1) -0.0355(1) -0.0253(1) 0.0662(1) 0.1691(1) 0.1745(1) 0.0818(1) 0.1254(2) 0.2784(2) 0.3786(2) 0.3658(1) 0.27996(9) 0.3828(1) 0.4312(2) 0.3929(1) 0.4389(1) 0.5626(1) 0.5999(1) 0.5432(2) 0.6083(2) 0.5837(2) 0.5875(2) 0.5905(4) 0.552(1) 0.0435(1) -0.11803(9) -0.19847(9) 0.0335(1) -0.0435(1) -0.1016(1) -0.0245(1) 0.0586(1) 0.0895(1) -0.0846(1) -0.1359(2) 0.1786(2) 0.2763(2)

0.0481(6) 0.0381(5) 0.0366(6) 0.0288(7) 0.0286(7) 0.0245(6) 0.0257(6) 0.0307(7) 0.0351(7) 0.0320(7) 0.0303(8) 0.076(1) 0.101(2) 0.099(1) 0.0639(8) 0.0536(7) 0.061(1) 0.0485(9) 0.0468(9) 0.0400(8) 0.054(1) 0.066(1) 0.043(1) 0.046(1) 0.112(2) 0.157(4) 0.16(2) 0.0443(7) 0.0341(6) 0.0451(6) 0.0385(8) 0.0295(7) 0.0350(7) 0.0315(7) 0.0312(7) 0.0370(8) 0.0385(8) 0.051(1) 0.0467(9) 0.106(2)

0.0321(6) 0.0362(6) 0.0480(7) 0.0296(8) 0.0296(7) 0.0282(7) 0.0311(7) 0.0375(8) 0.0350(8) 0.0417(9) 0.068(1) 0.048(1) 0.078(2) 0.071(1) 0.0639(8) 0.073(1) 0.054(1) 0.049(1) 0.0432(9) 0.051(1) 0.046(1) 0.044(1) 0.085(2) 0.093(2) 0.050(1) 0.111(3) 0.043(7) 0.0438(7) 0.0374(6) 0.0518(8) 0.0276(8) 0.0271(7) 0.0258(7) 0.0286(8) 0.0340(8) 0.0340(8) 0.0437(9) 0.058(1) 0.060(1) 0.122(2)

0.0522(7) 0.0373(6) 0.0398(6) 0.0404(8) 0.0328(7) 0.0313(7) 0.0332(7) 0.0309(7) 0.0339(8) 0.0497(9) 0.065(1) 0.040(1) 0.043(1) 0.0619(9) 0.0271(6) 0.0439(7) 0.0445(9) 0.0274(7) 0.0347(8) 0.0329(8) 0.0367(8) 0.048(1) 0.046(1) 0.064(1) 0.083(2) 0.103(3) 0.11(1) 0.0739(9) 0.0450(6) 0.0378(6) 0.0449(8) 0.0375(8) 0.0381(8) 0.0394(8) 0.0423(8) 0.0446(8) 0.0499(9) 0.060(1) 0.062(1) 0.065(2)

0.0129(5) 0.0070(4) 0.0135(5) 0.0036(6) 0.0049(6) 0.0011(5) 0.0049(6) 0.0027(6) 0.0028(6) 0.0126(7) 0.0115(8) 0.016(1) 0.008(2) 0.0394(9) 0.0190(7) 0.0159(7) 0.0224(9) 0.0137(8) 0.0105(7) 0.0097(7) 0.0018(8) 0.0129(9) 0.016(1) 0.001(1) 0.029(1) 0.076(3) 0.008(9) 0.0023(5) -0.0071(5) 0.0025(6) 0.0065(6) 0.0003(6) 0.0055(6) 0.0045(6) 0.0081(6) 0.0103(6) 0.0063(7) 0.0190(9) 0.0169(9) 0.048(2)

0.0174(5) 0.0151(4) 0.0195(5) 0.0140(6) 0.0115(5) 0.0083(5) 0.0100(5) 0.0072(6) 0.0100(6) 0.0143(7) 0.0118(8) 0.0118(9) 0.010(1) 0.0097(9) 0.0114(5) 0.0245(6) 0.0183(8) 0.0119(7) 0.0169(7) 0.0105(7) 0.0132(8) 0.0196(9) 0.0091(8) 0.019(1) 0.025(2) 0.071(3) 0.05(1) 0.0189(6) 0.0035(5) 0.0116(5) 0.0154(7) 0.0067(6) 0.0103(6) 0.0115(6) 0.0107(6) 0.0139(7) 0.0191(7) 0.0288(9) 0.0175(8) 0.036(2)

0.0197(5) 0.0247(5) 0.0237(5) 0.0170(7) 0.0194(6) 0.0150(6) 0.0190(6) 0.0175(6) 0.0129(7) 0.0278(8) 0.038(1) 0.0067(9) 0 . 0 1 1 ( 1 ) 0.0373(9) 0.0213(6) 0.0204(7) 0.0283(9) 0.0194(7) 0.0197(7) 0.0189(8) 0.0139(8) 0.0201(9) 0.026(1) 0.017(1) 0.020(1) 0.039(3) 0.026(8) 0.0383(7) 0.0180(5) 0.0133(6) 0.0188(7) 0.0148(6) 0.0157(6) 0.0177(7) 0.0196(7) 0.0222(7) 0.0260(8) 0.027(1) 0.044(1) 0.061(2)

Acknowledgment. We wish to thank the Deutsche Forschungsgemeinschaft, Bonn, for financial support.

References

1. Krämer, W.: Dimere 3-Hydroxy-o-chinone und der Mechanismus der Purpuragallinbildung. Dissertation, University of Mainz, Germany 1998.

2. Sheldrick, G. M.: SHELXL-97. Program for Crystal Structure Refine- ment. University of Göttingen, Germany 1997.

3. Altomare, Α.; Cascarano, G.; Giacovazzo, С.; Guagliardi, Α.; Burla, M.

е . ; Polidori, G.; Camalli, M.: S1R92 - a program for automatic solution of crystal structures by direct methods. J. Appi. Crystallogr. 27 (1994) 435-436.

4. Svenson, C.: CELSIUS. Program for Refinement of Lattice Parameters.

Lund, Sweden 1974.

5. Dräger, M.; Gattow G.: Kristallographische Computerprogramme für die CDC-3300. Acta Chem. Scand. 25 (1971) 761-762.